The utilization of high-sulfur coal is becoming more urgent due to the excessive utilization of low-sulfur,high-quality coal resources,and sulfur removal from high-sulfur coal is the most important issue.This paper re...The utilization of high-sulfur coal is becoming more urgent due to the excessive utilization of low-sulfur,high-quality coal resources,and sulfur removal from high-sulfur coal is the most important issue.This paper reviews the speciation,forms and distribution of sulfur in coal,the sulfur removal from raw coal,the thermal transformation of sulfur during coal pyrolysis,and the sulfur regulation during coal-blending coking of high organic-sulfur coals.It was suggested that the proper characterization of sulfur in coal cannot be obtained only by either chemical method or instrumental characterization,which raises the need of a combination of current or newly adopted characterization methods.Different from the removal of inorganic sulfur from coal,the organic sulfur can only be partly removed by chemical technologies;and the coal structure and property,particularly high-sulfur coking coals which have caking ability,may be altered and affected by the pretreatment processes.Based on the interactions among the sulfur radicals,sulfur-containing and hydrogen-containing fragments during coal pyrolysis and the reactions with minerals or nascent char,regulating the sulfur transformation behavior in the process of thermal conversion is the most effective way to utilize high organic-sulfur coals in the coke-making industry.An in-situ regulation approach of sulfur transformation during coal-blending coking has been suggested.That is,the high volatile coals with an appropriate releasing temperature range of CH4 overlapping well with that of H2 S from high organic-sulfur coals is blended with high organic-sulfur coals,and the C–S/C–C bonds in some sulfur forms are catalytically broken and immediately hydrogenated by the hydrogencontaining radicals generated from high volatile coals.Wherein,the effect of mass transfer on sulfur regulation during the coking process should be considered for the larger-scale coking tests through optimizing the ratios of different coals in the coal blend.展开更多
The changes in sulfur form in coal were analyzed by sulfur K-XANES(K-edge X-ray absorption near edge structures) spectra before and after the coal microwave desulfurization in a Na OH solution. After the desulfurizati...The changes in sulfur form in coal were analyzed by sulfur K-XANES(K-edge X-ray absorption near edge structures) spectra before and after the coal microwave desulfurization in a Na OH solution. After the desulfurization, the pyritic sulfur content of coal decreased significantly from 53.6% to 39.2%, while the sulfate sulfur content increased from 17.3% to 34.6%. Only a small amount of thiophene sulfur(20.1–16.1%) was removed. Some sulfur-containing components were oxidized to sulfate sulfur. Under the optimum conditions, the ash content decreased, while the volatile content increased. The calorific value of coal slightly decreased with a slight variation in the amplitudes. The overall structure of coal did not change significantly based on Fourier transform infrared(FTIR) spectral analyses. Thus, the desulfurization of coal with microwave irradiation in a Na OH solution did not significantly change the properties of coal.展开更多
The Tianqiao Pb-Zn ore deposit of Guizhou Province, China, is located in the mid-east of the Sichuan-Yunnan-Guizhou Pb-Zn-Ag multi-metallic mineralization area, which is representative of the Pb-Zn ore de-posits in th...The Tianqiao Pb-Zn ore deposit of Guizhou Province, China, is located in the mid-east of the Sichuan-Yunnan-Guizhou Pb-Zn-Ag multi-metallic mineralization area, which is representative of the Pb-Zn ore de-posits in this area. It consists of three main orebodies, whose Pb+Zn reserves are more than 0.2 million ton. This paper analyzes the sulfur isotopic composition of these orebodies. The data show that the ore minerals (galena, sphalerite, pyrite) in these orebodies are enriched in heavy sulfur, with δ34SV-CDT values varying between 8.35‰ and 14.44‰, i.e. the δ34SV-CDT values of pyrite are between 12.81‰ and 14.44‰, the mean value is 13.40‰; the δ34SV-CDT values of sphalerite are range from 10.87‰ to 14.00‰, the mean value is 12.53‰; the δ34SV-CDT values of galena are range from 8.35‰ to 9.83‰, the mean value is 8.84‰, and they have the feature of δ34Spyrite>δ34Ssphalerite>δ34Sgalena, which indicates the sulfur isotope in ore-forming fluids has attained equilibrium. The δ34S V-CDT values of the deposit are close to those of sulfates from carbonate strata of different ages in the ore-field (15‰), which suggests that the sulfur in the ore-forming fluids should be derived from the thermo-chemical sulfate reduction of sulfates from the sedimentary strata.展开更多
The Bainiuchang deposit in Yunnan Province, China, is located geographically between the Gejiu ore field and the Dulong ore field. In addition to >7000 t Ag reserves, the deposit possesses large-scale Pb, Zn, Sn re...The Bainiuchang deposit in Yunnan Province, China, is located geographically between the Gejiu ore field and the Dulong ore field. In addition to >7000 t Ag reserves, the deposit possesses large-scale Pb, Zn, Sn reserves and a mass of dispersed elements (i.e., In, Cd, Ge, Ga, etc.). Based on systematic studies of sulfur isotopic composition, the authors conclude: The Bainiuchang deposit experienced two epochs of metallogenesis, i.e., the Middle-Cambrian sea-floor exhalative sedimentary metallogenic epoch and the Yanshanian magmatic hydrothermal superimposition metallogenic epoch. In the two metallogenic epochs, the δ34S values of sulfides were all near 0, showing a tendency of being enriched slightly in heavy sulfur. The δ34S values of sulfides in the early metallogenic epoch are within the range of 2‰–5‰ with a peak value range of 2‰–3‰ and an average of 3.0‰, and those of sulfides in the late metallogenic epoch are within the range of 2‰–6‰ with a peak value of 3‰–4‰ and an average of 3.9‰. For the single metallogenic epoch, sulfur in the ore-forming fluids in the early epoch already reached isotopic equilibrium and was derived mainly from underneath the magma chamber or basement metamorphic igneous rocks. Sulfur in the sulfides in the late epoch was derived mainly from magmatic hydrothermal fluids formed in the process of remelting of the basement metamorphic igneous rocks.展开更多
1 Introduction On the territory Kulunda Plain,located to the south-west of the Ob’plateau,there are more than 3,000 fresh and salt lakes with water TDS range from 1 to 430 g/L.The interest in these lakes was associat...1 Introduction On the territory Kulunda Plain,located to the south-west of the Ob’plateau,there are more than 3,000 fresh and salt lakes with water TDS range from 1 to 430 g/L.The interest in these lakes was associated mainly with the study of展开更多
No. 22 ore of Dafulou deposit was systematically analyzed for sulfur isotopes. The results show that the δ34S values of sulfide minerals, ranging from 0.154 to +0.218% and with an average value of +0.114 1%, are most...No. 22 ore of Dafulou deposit was systematically analyzed for sulfur isotopes. The results show that the δ34S values of sulfide minerals, ranging from 0.154 to +0.218% and with an average value of +0.114 1%, are mostly positive and characterized by rich sulfur(S) content. This suggests that the sulfur of the Dafulou ore deposit is derived from magma and relates to the Longxianggai concealed granite, which points to the important role of magma during mineralization and implyies the product of the active continental margin. By comparison between the Dafulou and the Kengma tin deposit, significant differences exist in the sulfur isotope composition. In the Kengma deposit, the sulfur isotope composition is characterized by the high negative value, which is different from the Dafulou tin-polymetallic deposit. The difference of the enrichment and fractionation of the sulfur isotope is the synthesized result of the metallogenic conditions. It also has the difference in the metallogenic environment and metallogenic characteristics of the deposit in the same ore belt.展开更多
Lithium–sulfur(Li–S) batteries represent a "beyond Li-ion" technology with low cost and high theoretical energy density and should fulfill the ever-growing requirements of electric vehicles and stationary ...Lithium–sulfur(Li–S) batteries represent a "beyond Li-ion" technology with low cost and high theoretical energy density and should fulfill the ever-growing requirements of electric vehicles and stationary energy storage systems. However, the sulfur-based conversion reaction in conventional liquid electrolytes results in issues like the so-called shuttle effect of polysulfides and lithium dendrite growth, which deteriorate the electrochemical performance and safety of Li–S batteries. Optimization of conventional organic solvents(including ether and carbonate) by fluorination to form fluorinated electrolytes is a promising strategy for the practical application of Li–S batteries. The fluorinated electrolytes, owing to the high electronegativity of fluorine, possesses attractive physicochemical properties, including low melting point,high flash point, and low solubility of lithium polysulfide, and can form a compact and stable solid electrolyte interphase(SEI) with the lithium metal anode. Herein, we review recent advancements in the development of fluorinated electrolytes for use in Li–S batteries. The effect of solvent molecular structure on the performance of Li–S batteries and the formation mechanism of SEI on the cathode and anode sides are analyzed and discussed in detail. The remaining challenges and future perspectives of fluorinated electrolytes for Li–S batteries are also presented.展开更多
天马山硫金矿是铜陵矿集区典型的层控热液叠加改造型矿床,层状矿体中发育大量的矽卡岩矿物。为查明该矿床中矽卡岩矿物的类型及形成环境,探讨矽卡岩与硫、金成矿之间的关系,对主要的矽卡岩矿物开展了矿物学及矿物化学研究,并对矿石进行...天马山硫金矿是铜陵矿集区典型的层控热液叠加改造型矿床,层状矿体中发育大量的矽卡岩矿物。为查明该矿床中矽卡岩矿物的类型及形成环境,探讨矽卡岩与硫、金成矿之间的关系,对主要的矽卡岩矿物开展了矿物学及矿物化学研究,并对矿石进行了硫同位素地球化学研究。研究表明:矿区内的矽卡岩矿物以石榴子石和辉石为主,其中石榴子石以钙铁榴石为主,属于钙铁榴石-钙铝榴石固熔体系列(Gro 0~18.73 And 80.54~99.00 Spe+Pyr+Alm 0.54~1.47);辉石以透辉石为主,其次为钙铁辉石,属于透辉石-钙铁辉石系列(Di 62.35~97.65 Hd 1.89~36.27 Jo 0.31~1.55)。天马山硫金矿的矿物组合(钙铁辉石+透辉石)属于氧化型矽卡岩,表明矽卡岩形成于相对高温和高氧逸度的条件。石榴子石和辉石端元组分特征及辉石Mn/Fe值(0.02~0.07)具有典型的矽卡岩型铜、金矿床特征。矿石硫同位素具有岩浆源的特征,与区内燕山期岩浆-成矿作用形成的矿石一致,而明显区别于喷流-沉积作用形成的矿石,显示成矿作用与燕山期岩浆活动具有密切的成因联系。燕山期中酸性岩浆交代碳酸盐岩围岩形成大量矽卡岩,矽卡岩矿物的形成增加了岩石的孔隙度和渗透率,为晚期硫、金矿床的形成提供了有利条件。展开更多
基金financial support of National Natural Science Foundation of China(U1910201,21878208)Transformation of Scientific and Technological Achievements Programs of Higher Education Institutions in Shanxi(TSTAP)Shanxi Province Science Foundation for Key Program(201901D111001(ZD))。
文摘The utilization of high-sulfur coal is becoming more urgent due to the excessive utilization of low-sulfur,high-quality coal resources,and sulfur removal from high-sulfur coal is the most important issue.This paper reviews the speciation,forms and distribution of sulfur in coal,the sulfur removal from raw coal,the thermal transformation of sulfur during coal pyrolysis,and the sulfur regulation during coal-blending coking of high organic-sulfur coals.It was suggested that the proper characterization of sulfur in coal cannot be obtained only by either chemical method or instrumental characterization,which raises the need of a combination of current or newly adopted characterization methods.Different from the removal of inorganic sulfur from coal,the organic sulfur can only be partly removed by chemical technologies;and the coal structure and property,particularly high-sulfur coking coals which have caking ability,may be altered and affected by the pretreatment processes.Based on the interactions among the sulfur radicals,sulfur-containing and hydrogen-containing fragments during coal pyrolysis and the reactions with minerals or nascent char,regulating the sulfur transformation behavior in the process of thermal conversion is the most effective way to utilize high organic-sulfur coals in the coke-making industry.An in-situ regulation approach of sulfur transformation during coal-blending coking has been suggested.That is,the high volatile coals with an appropriate releasing temperature range of CH4 overlapping well with that of H2 S from high organic-sulfur coals is blended with high organic-sulfur coals,and the C–S/C–C bonds in some sulfur forms are catalytically broken and immediately hydrogenated by the hydrogencontaining radicals generated from high volatile coals.Wherein,the effect of mass transfer on sulfur regulation during the coking process should be considered for the larger-scale coking tests through optimizing the ratios of different coals in the coal blend.
基金provided by the National Natural Science Foundation of China(No.51274199)the Specialized Research Fund for the Doctoral Program of Higher Education(No.20130095110008)
文摘The changes in sulfur form in coal were analyzed by sulfur K-XANES(K-edge X-ray absorption near edge structures) spectra before and after the coal microwave desulfurization in a Na OH solution. After the desulfurization, the pyritic sulfur content of coal decreased significantly from 53.6% to 39.2%, while the sulfate sulfur content increased from 17.3% to 34.6%. Only a small amount of thiophene sulfur(20.1–16.1%) was removed. Some sulfur-containing components were oxidized to sulfate sulfur. Under the optimum conditions, the ash content decreased, while the volatile content increased. The calorific value of coal slightly decreased with a slight variation in the amplitudes. The overall structure of coal did not change significantly based on Fourier transform infrared(FTIR) spectral analyses. Thus, the desulfurization of coal with microwave irradiation in a Na OH solution did not significantly change the properties of coal.
基金supported by the National Basic Research Program of China (No. 2007CB411402)the National Natural Science Foundation of China (Grant No. 40573036)
文摘The Tianqiao Pb-Zn ore deposit of Guizhou Province, China, is located in the mid-east of the Sichuan-Yunnan-Guizhou Pb-Zn-Ag multi-metallic mineralization area, which is representative of the Pb-Zn ore de-posits in this area. It consists of three main orebodies, whose Pb+Zn reserves are more than 0.2 million ton. This paper analyzes the sulfur isotopic composition of these orebodies. The data show that the ore minerals (galena, sphalerite, pyrite) in these orebodies are enriched in heavy sulfur, with δ34SV-CDT values varying between 8.35‰ and 14.44‰, i.e. the δ34SV-CDT values of pyrite are between 12.81‰ and 14.44‰, the mean value is 13.40‰; the δ34SV-CDT values of sphalerite are range from 10.87‰ to 14.00‰, the mean value is 12.53‰; the δ34SV-CDT values of galena are range from 8.35‰ to 9.83‰, the mean value is 8.84‰, and they have the feature of δ34Spyrite>δ34Ssphalerite>δ34Sgalena, which indicates the sulfur isotope in ore-forming fluids has attained equilibrium. The δ34S V-CDT values of the deposit are close to those of sulfates from carbonate strata of different ages in the ore-field (15‰), which suggests that the sulfur in the ore-forming fluids should be derived from the thermo-chemical sulfate reduction of sulfates from the sedimentary strata.
基金supported jointly by the Major Orientation Research Project (No. KZCX2-YW-111) of CASNational Basic Research Program of China (No. 2007CB411408)the National Natural Science Foundation of China (No. 40872074)
文摘The Bainiuchang deposit in Yunnan Province, China, is located geographically between the Gejiu ore field and the Dulong ore field. In addition to >7000 t Ag reserves, the deposit possesses large-scale Pb, Zn, Sn reserves and a mass of dispersed elements (i.e., In, Cd, Ge, Ga, etc.). Based on systematic studies of sulfur isotopic composition, the authors conclude: The Bainiuchang deposit experienced two epochs of metallogenesis, i.e., the Middle-Cambrian sea-floor exhalative sedimentary metallogenic epoch and the Yanshanian magmatic hydrothermal superimposition metallogenic epoch. In the two metallogenic epochs, the δ34S values of sulfides were all near 0, showing a tendency of being enriched slightly in heavy sulfur. The δ34S values of sulfides in the early metallogenic epoch are within the range of 2‰–5‰ with a peak value range of 2‰–3‰ and an average of 3.0‰, and those of sulfides in the late metallogenic epoch are within the range of 2‰–6‰ with a peak value of 3‰–4‰ and an average of 3.9‰. For the single metallogenic epoch, sulfur in the ore-forming fluids in the early epoch already reached isotopic equilibrium and was derived mainly from underneath the magma chamber or basement metamorphic igneous rocks. Sulfur in the sulfides in the late epoch was derived mainly from magmatic hydrothermal fluids formed in the process of remelting of the basement metamorphic igneous rocks.
基金supported by the project of RFBR No 13-05 -00556
文摘1 Introduction On the territory Kulunda Plain,located to the south-west of the Ob’plateau,there are more than 3,000 fresh and salt lakes with water TDS range from 1 to 430 g/L.The interest in these lakes was associated mainly with the study of
基金Project(41202051) supported by the National Natural Science Foundation of ChinaProject(2012M521721) supported by China Postdoctoral Science FoundationProject(CSUZC2013021) supported by Valuable Equipment Open Sharing Fund of Central South University,China
文摘No. 22 ore of Dafulou deposit was systematically analyzed for sulfur isotopes. The results show that the δ34S values of sulfide minerals, ranging from 0.154 to +0.218% and with an average value of +0.114 1%, are mostly positive and characterized by rich sulfur(S) content. This suggests that the sulfur of the Dafulou ore deposit is derived from magma and relates to the Longxianggai concealed granite, which points to the important role of magma during mineralization and implyies the product of the active continental margin. By comparison between the Dafulou and the Kengma tin deposit, significant differences exist in the sulfur isotope composition. In the Kengma deposit, the sulfur isotope composition is characterized by the high negative value, which is different from the Dafulou tin-polymetallic deposit. The difference of the enrichment and fractionation of the sulfur isotope is the synthesized result of the metallogenic conditions. It also has the difference in the metallogenic environment and metallogenic characteristics of the deposit in the same ore belt.
基金the National Natural Science Foundation of China(Grant nos.51772089 and 21872046)the Youth 1000 Talent Program of China(Grant no.S2017JJJCQN0149)+2 种基金the Fundamental Research Funds for the Central Universitiesthe Outstanding Youth Scientist Foundation of Hunan Province(Grant no.S2019JJQNJJ0361)Natural Science Foundation of Hunan Province(Grant no.S2019JJQNJJ0361)。
文摘Lithium–sulfur(Li–S) batteries represent a "beyond Li-ion" technology with low cost and high theoretical energy density and should fulfill the ever-growing requirements of electric vehicles and stationary energy storage systems. However, the sulfur-based conversion reaction in conventional liquid electrolytes results in issues like the so-called shuttle effect of polysulfides and lithium dendrite growth, which deteriorate the electrochemical performance and safety of Li–S batteries. Optimization of conventional organic solvents(including ether and carbonate) by fluorination to form fluorinated electrolytes is a promising strategy for the practical application of Li–S batteries. The fluorinated electrolytes, owing to the high electronegativity of fluorine, possesses attractive physicochemical properties, including low melting point,high flash point, and low solubility of lithium polysulfide, and can form a compact and stable solid electrolyte interphase(SEI) with the lithium metal anode. Herein, we review recent advancements in the development of fluorinated electrolytes for use in Li–S batteries. The effect of solvent molecular structure on the performance of Li–S batteries and the formation mechanism of SEI on the cathode and anode sides are analyzed and discussed in detail. The remaining challenges and future perspectives of fluorinated electrolytes for Li–S batteries are also presented.
文摘天马山硫金矿是铜陵矿集区典型的层控热液叠加改造型矿床,层状矿体中发育大量的矽卡岩矿物。为查明该矿床中矽卡岩矿物的类型及形成环境,探讨矽卡岩与硫、金成矿之间的关系,对主要的矽卡岩矿物开展了矿物学及矿物化学研究,并对矿石进行了硫同位素地球化学研究。研究表明:矿区内的矽卡岩矿物以石榴子石和辉石为主,其中石榴子石以钙铁榴石为主,属于钙铁榴石-钙铝榴石固熔体系列(Gro 0~18.73 And 80.54~99.00 Spe+Pyr+Alm 0.54~1.47);辉石以透辉石为主,其次为钙铁辉石,属于透辉石-钙铁辉石系列(Di 62.35~97.65 Hd 1.89~36.27 Jo 0.31~1.55)。天马山硫金矿的矿物组合(钙铁辉石+透辉石)属于氧化型矽卡岩,表明矽卡岩形成于相对高温和高氧逸度的条件。石榴子石和辉石端元组分特征及辉石Mn/Fe值(0.02~0.07)具有典型的矽卡岩型铜、金矿床特征。矿石硫同位素具有岩浆源的特征,与区内燕山期岩浆-成矿作用形成的矿石一致,而明显区别于喷流-沉积作用形成的矿石,显示成矿作用与燕山期岩浆活动具有密切的成因联系。燕山期中酸性岩浆交代碳酸盐岩围岩形成大量矽卡岩,矽卡岩矿物的形成增加了岩石的孔隙度和渗透率,为晚期硫、金矿床的形成提供了有利条件。
